Carbon nanotube/dendrimer hybrids as electrodes for supercapacitors

Journal of Solid State Electrochemistry - Carbon nanotubes (CNTs) were surface-modified by a glycodendrimer with four glucose units (4-Gl). Electrodes for supercapacitors based on CNT/4-Gl hybrids...     

Glass/PDMS hybrid microfluidic device integrating vertically aligned SWCNTs to ultrasensitive electrochemical determinations

This communication reports a promising platform for rapid, simple, direct, and ultrasensitive determination of serotonin. The method is related to integration of vertically aligned single-walled carbon nanotubes (SWCNTs) in electrochemical microfluidic devices. The required microfabrication protocol is simple and fast. In addition, the nanomaterial influenced remarkably the obtained limit-of-detection (LOD) values. Our system achieved a LOD of 0.2 nmol L(-1) for serotonin, to the best of our knowledge one of the lowest values reported in the literature.     

Kinetics and thermodynamics of chlorpromazine interaction with lipid bilayers: effect of charge and cholesterol

Passive transport across cell membranes is the major route for the permeation of xenobiotics through tight endothelia such as the blood–brain barrier. The rate of passive permeation through lipid bilayers for a given drug is therefore a critical step in the prediction of its pharmacodynamics. We describe a detailed study on the kinetics and thermodynamics for the interaction of chlorpromazine (CPZ), an antipsychotic drug used in the treatment of schizophrenia, with neutral and negatively charged lipid bilayers. Isothermal titration calorimetry was used to study the partition and translocation of CPZ in lipid membranes composed of pure POPC, POPC:POPS (9:1), and POPC:Chol:POPS (6:3:1). The membrane charge due to the presence of POPS as well as the additional charge resulting from the introduction of CPZ in the membrane were taken into account, allowing the calculation of the intrinsic partition coefficients (K(P)) and the enthalpy change (ΔH) associated with the process. The enthalpy change upon partition to all lipid bilayers studied is negative, but a significant entropy contribution was also observed for partition to the neutral membrane. Because of the positive charge of CPZ, the presence of negatively charged lipids in the bilayer increases both the observed amount of CPZ that partitions to the membrane (KP(obs)) and the magnitude of ΔH. However, when the electrostatic effects are discounted, the intrinsic partition coefficient was smaller, indicating that the hydrophobic contribution was less significant for the negatively charged membrane. The presence of cholesterol strongly decreases the affinity of CPZ for the bilayer in terms of both the amount of CPZ that associates with the membrane and the interaction enthalpy. A quantitative characterization of the rate of CPZ translocation through membranes composed of pure POPC and POPC:POPS (9:1) was also performed using an innovative methodology developed in this work based on the kinetics of the heat evolved due to the interaction of CPZ with the membranes.     

MALDI-MS detection of noncovalent interactions of single stranded DNA with Escherichia coli single-stranded DNA-binding protein

The Escherichia coli single-stranded DNA binding protein (SSB) selectively binds single-stranded (ss) DNA and participates in the process of DNA replication, recombination and repair. Different binding modes have previously been observed in SSB?ssDNA complexes, due to the four potential binding sites of SSB. Here, chemical cross-linking, combined with high-mass matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), is used to determine the stoichiometry of the SSB?ssDNA complex. SSB forms a stable homotetramer in solution, but only the monomeric species (m/z 19,100) can be detected with standard MALDI-MS. With chemical cross-linking, the quaternary structure of SSB is conserved, and the tetramer (m/z 79,500) was observed. We found that ssDNA also functions as a stabilizer to conserve the quaternary structure of SSB, as evidenced by the detection of a SSB?ssDNA complex at m/z 94,200 even in the absence of chemical cross-linking. The stability of the SSB?ssDNA complex with MALDI strongly depends on the length and strand of oligonucleotides and the stoichiometry of the SSB?ssDNA complex, which could be attributed to electrostatic interactions that are enhanced in the gas phase. The key factor affecting the stoichiometry of the SSB?ssDNA complex is how ssDNA binds to SSB, rather than the protein-to-DNA ratio. This further suggests that detection of the complex by MALDI is a result of specific binding, and not due to non-specific aggregation in the MALDI plume.     

Ergodicity breaking and parametric resonances in systems with long-range interactions

We explore the mechanism responsible for the ergodicity breaking in systems with long-range forces. In thermodynamic limit such systems do not evolve to the Boltzmann-Gibbs equilibrium, but become trapped in an out-of-equilibrium quasi-stationary-state. Nevertheless, we show that if the initial distribution satisfies a specific constraint-a generalized virial condition-the quasistationary state is very close to ergodic and can be described by Lynden-Bell statistics. On the other hand, if the generalized virial condition is violated, parametric resonances are excited, leading to chaos and ergodicity breaking.     

Is a system's wave function in one-to-one correspondence with its elements of reality?

Although quantum mechanics is one of our most successful physical theories, there has been a long-standing debate about the interpretation of the wave function--the central object of the theory. Two prominent views are that (i) it corresponds to an element of reality, i.e., an objective attribute that exists before measurement, and (ii) it is a subjective state of knowledge about some underlying reality. A recent result [M.?F. Pusey, J. Barrett, and T. Rudolph, arXiv:1111.3328] has placed the subjective interpretation into doubt, showing that it would contradict certain physically plausible assumptions, in particular, that multiple systems can be prepared such that their elements of reality are uncorrelated. Here we show, based only on the assumption that measurement settings can be chosen freely, that a system's wave function is in one-to-one correspondence with its elements of reality. This also eliminates the possibility that it can be interpreted subjectively.     

Structure of long-term average frequencies for kuramoto oscillator systems

We study the long-term average frequency as a function of the natural frequency for Kuramoto oscillators with periodic coefficients. Unlike the case for more general periodically forced oscillators, this function is never a "devil's staircase"; it may have plateaus at integer multiples of the forcing frequency, but we prove it is strictly increasing between these plateaus. The proof uses the fact that the flow maps for Kuramoto oscillators extend to M?bius transformations on the complex plane, and that M?bius transformations have particularly simple dynamics that rule out p∶q mode locking except in the case of fixed points (q=1). We also give a criterion for the degeneration of an integer plateau to a single point and use it to explain the absence of plateaus at even multiples of the collective frequency for a Kuramoto system with a bimodal frequency distribution.